JP2015520776A - Degradable materials derived from biological components - Google Patents

Abstract

Biodegradable material-derived degradable material comprising 10-60% by weight protein adhesive (1) from at least one protein and 2-50% by weight natural fiber (4). Furthermore, at least one hygroscopic inorganic material (7) 2 to 15% by mass, water (2) 10 to 55% by mass and additive component (5) 0 to 50% by mass are present in the material (10).

Description

TECHNICAL FIELD The present invention relates to a degradable material derived from a biological component and a method for producing a molded member from the degradable material.

Prior art
US 7,387,756 (Guilbert et al.) Describes a method for producing natural fiber-based materials. Natural fibers are mixed with a natural protein binder in powder form, where the natural fibers have a moisture content of 1-15%. The moisture content is adjusted to 6-24% and the mixture is subsequently shaped by a hot pressing process.

  US 6,284,838 (Novamont SpA) discloses a biodegradable composition from lignin or lignin-containing material and protein. Said composition may comprise further additives. The lignin or lignin-containing material is heated with the protein and melted. Fine wood particles can also be used as the lignin-containing material. As preferred protein, vegetable or animal casein or gelatin is used.

  US 5,360,586 (Wyatt Danny) describes a method for producing degradable molded parts derived from cellulose-containing materials. The cellulose-containing material contains less than 50% water and is mixed with a binder and a blowing agent. This mixture is filled into an extruder, mixed with water and subsequently extruded into molded parts.

  DE 461 775 (Hans Brandt) discloses a wood substitute material that is cheaper and lighter than wood and exhibits a higher flash point and higher water resistance. For the production of the material, the paper is boiled in an aqueous potassium hydroxide solution and subsequently mixed with tannic acid and sodium hydroxide. The material is dried to a powder. Subsequently, the powder is mixed with cement, sodium carbonate, talc and antimony chloride and the hydrogen sulfide solution of the skin is mixed under stirring. The generated material is drawn on a plate or press-molded to form a molded product.

  DE 334 183 (Dr. Kukula) describes a wood substitute material for producing pencil stems (Bleistiftfassung). The material is made from a mixture of wood fiber, inorganic material and water. As a binder, glue and dextrin or plant mucilage is added to the mixture. The material is pressed in a suitable mold under mild pressure without heating. Examples include 4-5 parts by weight of ground pulp or sawdust (a small amount of pulp may be added), 1 part by weight of asbestos, diatomaceous earth or talc and 1 part by weight of bone glue or gelatin and 1 part by weight of plant mucous. It is mentioned that the mass or dextrin may be mixed with the addition of as little water as possible.

  WO 2009/079579 (E2E Materials) describes biodegradable, formaldehyde-free cardboard, in particular cardboard with an adhesive derived from soybeans. The cardboard consists of a first plate made from soy resin and a further plate derived from plant fiber material. The first plate is connected to a wave element. Plant fibers may include flax, clam, ramie, sisal, jute, cotton, banana, pineapple or kenaf fibers. The fiber may be present as a woven or non-woven fabric. Preferably, however, the fibers are present as a nonwoven mat bound with a natural binder, such as polylactide. Said wavy elements are preferably made from pop kernels, in particular wheat, rice or corn kernels. In the first step of the production process, a first number of plates made of vegetable fiber is impregnated with soy resin, dried, pressed together into a press plate and subsequently bonded to the undulating element. Finally, a second press plate is provided on the corrugated element and bonded. The soy resin may further comprise a polysaccharide, in particular agar, gellan or mixtures thereof.

  WO 2004/0291 35 (K.U. Leuven) discloses gluten-based biopolymers and fiber composites coated with gluten. The material is produced by mixing gluten with molecules containing a plurality of thiol groups. Gluten is therefore preferably dispersed together with the molecules in an aqueous solution. In addition, the fibers may also be coated with gluten and processed into a composite material. The fiber may be synthetic or natural. In a special embodiment, gluten bridges are formed around the fibers. The fiber matrix thus obtained may subsequently be pressed in a pressure casting process. As fibers, on the one hand, cellulose fibers or stems, hulls, pods or fruits may be used on the one hand.

  The disadvantages of the known materials are that molded parts made from said materials first have little mechanical stability, since their curing takes some time, especially in the presence of protein adhesives. It is. Furthermore, the material must be processed in waste because not all materials used are degradable and environmentally friendly.

DESCRIPTION OF THE INVENTION The object of the present invention is to cure more rapidly compared to materials known from the prior art, so that the molded parts produced have good mechanical stability as quickly as possible, and To create materials belonging to the technical fields mentioned in the introduction, which can be completely dissolved and decomposable.

  The solution to the problem is defined in the characterizing part of claim 1. According to the invention, the material contains 10-60% by weight of protein adhesive from at least one protein. Furthermore, the degradable material contains 2 to 50% by mass of natural fibers, 2 to 15% by mass of at least one hygroscopic inorganic material, and 10 to 55% by mass of water. Furthermore, additive components may be present in the material in an amount of 0 to 50% by weight.

  The material of the present invention is “degradable”. In the meaning of the present application, “degradable” is understood to mean that the material can be completely auffloesed through a biological process.

  As “protein adhesive”, in the sense of the present application, a protein solution is understood that can form a three-dimensional cross-link through a curing process. The curing process is preferably reversible, in particular by water addition and additional thermal action. Preferably, the protein adhesive consists of only one protein or only one protein class. Alternatively, the protein adhesive may consist of a plurality of different proteins or proteins of different protein classes.

  Said material comprises 10-60% by weight, preferably 30-50% by weight, particularly preferably 40-45% by weight of protein adhesive.

  The material further comprises 2 to 50% by weight, preferably 5 to 35% by weight, particularly preferably 7 to 20% by weight, of natural fibers.

  Furthermore, 2-15% by weight, preferably 5-12% by weight, particularly preferably 7-10% by weight of at least one hygroscopic inorganic material and 10-55% by weight, preferably 20-50% by weight, particularly preferably. 35-45% by weight of water is present in the degradable material. The hygroscopic inorganic material is particularly preferably present in the material in powder form.

  Furthermore, the material may contain additive components in an amount of 0-50% by weight, preferably 10-40% by weight, particularly preferably 20-30% by weight. The additive component need not necessarily be present in the material. The material of the present invention further solves the above-mentioned technical problem without an additive component.

  By the addition of the hygroscopic inorganic material, the water present in the material is added to the hygroscopic inorganic material as crystal water, thereby increasing the curing rate of the protein adhesive. Furthermore, the hygroscopic inorganic material may additionally bind to water, so that the molded part produced from the material is relatively quick and good even before complete curing of the protein adhesive. Resulting in having mechanical stability.

An essential advantage of the material of the present invention is that it is completely soluble in hot water. Based on the material composition derived from pure natural substances, the resulting aqueous solution can be treated as sewage without problems or used for plant fertilization. Alternatively, a molded part made from said material may be burned for processing, in which case a nearly neutral CO ₂ balance results as a result of the use of recycled raw materials. Furthermore, the material of the present invention may be used as compost after use.

  The degradable material is initially in liquid form and is therefore very easily processed into a shaped part, for example by pressing or extrusion. Furthermore, it was confirmed that the material of the present invention is used as a substrate for a 3D printer.

  As hygroscopic inorganic materials, preferably at least one of the following substances is used: aluminum hydroxide, bentonite, calcium sulfate, calcium chloride, calcium carbonate, calcium oxide, calcium hydroxide, calcium aluminate, calcium silicate, silica Potassium acid, potassium carbonate, silicic acid, lithium silicate, magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium hydrogen sulfate, magnesium silicate, sodium sulfate, sodium acetate, sodium hydrogen sulfate, pentasodium triphosphate, sepiolite, silica gel ( Silica gel), silicon dioxide, zeolite. The hygroscopic inorganic material more preferably comprises a mixture of at least two of the aforementioned substances.

  Calcium sulfate is particularly preferably used in the form of commercially available gypsum powder, while lithium silicate, sodium silicate and potassium silicate are preferably used in the form of so-called amorphous “water glass”. As the zeolite, so-called molecular sieves are used, preferably molecular sieves having a pore size of 3 Å.

  The protein adhesive preferably comprises Glutin, collagen, alginate, albumin, gelatin, chondrin, agar, xanthan or mixtures thereof. Glutin-derived protein adhesives are relatively easily produced from animal bone, cartilage or skin. As a collagen adhesive, a large amount of gelatin obtained from the food industry can be used. Alginates can be used in the materials according to the invention, in particular as powdered salts of alginic acid, such as sodium alginate, potassium alginate, ammonium alginate or calcium alginate.

  Furthermore, in addition to protein adhesives, lignin sulfonate, lignin, glucose or dextrin can be used as further binders.

  Alternatively, further protein adhesives can also be used in the material of the invention, for example fibrin adhesives or mussel derived adhesion proteins. However, since these protein adhesives are currently available only in small amounts and at a high price, they are not economically worthy of incorporation into the materials of the present invention.

  Preferably, bone glue, glue, rabbit glue or fish glue is used as the protein adhesive. These glues themselves are readily available in large quantities and are even cheaper. Furthermore, its use is easy because of its relatively low melting point, because the material does not need to be heated to high temperatures for manufacturing and application.

  Natural fibers preferably include wood fibers, cereal fibers, nutshell fibers, glass fibers, corn meal, cellulose fibers, cellulose aggregates or mixtures thereof.

  Such natural fibers are generated as waste products in the agriculture, forestry and pulp industries. Particularly preferably, softwood fibers are used as natural fibers. Natural fibers may have different sizes depending on the molded part to be produced by the material. Natural fibers having a length of preferably 0.5 mm to 50 mm are used. Alternatively, however, natural fibers may be used in powder form, for example as a powder having an average particle size of 0.01 mm to 0.5 mm. Such a powder may be produced, for example, by crushing natural fibers. Natural fibers can withstand the greater loads by imparting the necessary mechanical strength to the cured material, for example when a chair or desk is made from the cured material.

  The fiber can be used in its natural state or alternatively after chemical modification. For example, cellulose fibers can be chemically altered by methylation, sulfonation, nitration, acetylation, etc. before being used for the materials of the present invention.

  Basically, all kinds of plant fibers are used in the material according to the invention, for example bamboo fibers, Asa fibers, Reisschalenfaser or the like.

  As the hygroscopic inorganic material, calcium sulfate, magnesium sulfate or a mixture thereof is preferably used. Particularly preferably, the hygroscopic inorganic material is used in the form of a powder. Commercially available gypsum powder is preferably used as calcium sulfate. Both calcium sulfate and magnesium sulfate are very hygroscopic and bind the water of the material as crystal water. This reduces the amount of unbound water present in the material, thereby accelerating the hardening of the protein adhesive. The use of calcium sulfate further increases the stability of molded parts made from the material, because calcium sulfate additionally binds to the water of the material, thereby forming a mechanically stable structure. .

  The preferred action of the hygroscopic inorganic material is to bind free water present in the material. Therefore, it will be apparent to those skilled in the art that it is desirable to use a hygroscopic inorganic material in a water-free form as much as possible for the production of the material. Preferably, therefore, it is desirable to use calcium sulfate as anhydride and water-free magnesium sulfate or magnesium sulfate monohydrate.

  A further advantage of the hygroscopic inorganic material is the heat generation of crystal water penetration (Kristallwassereinlagerung). The released thermal energy promotes the hardening of the protein adhesive, which results in a good rapid solidification of the material.

  The additive component preferably comprises 1-10% by weight, preferably 2-8% by weight, of at least one biodegradable plasticizer. The biodegradable plasticizer is preferably glycerin, urea, citric acid triethyl ester, sorbitol, xanthan or alkyl citrate. By adding a plasticizer, the brittleness of the material can be changed. For example, the elasticity of a molded member manufactured from the material can be modified.

  Alternatively, conventional plasticizers can also be used, for example conventional plasticizers known from the polymer industry. However, such plasticizers are not without environmental concerns.

  The additive component preferably comprises 0.1 to 10% by weight, particularly preferably 3 to 6% by weight, of at least one biodegradable stabilizer. The degradable stabilizer is preferably lignin sulfonate, linseed oil or boiled linseed oil (Leinoelfirnis). By adding the stabilizer, the flow properties of the material can be improved. Lignin sulfonate reacts with the protein adhesive protein, while linseed oil and boiled linseed oil both harden by oxidation. The reaction of both serves to impart further mechanical stability to the material. Furthermore, both reactions protect the material from moisture, so that damage or softening of the material can be prevented during unexpected liquid contact.

  The additive component preferably further comprises at least one 0.1 to 10% by weight water resistance improver. Particularly preferably, tannin, corilagin, ganidine, potassium alum, urea, casein, ferulic acid, gossypol, sulfonic acid, enzymes such as lysyl oxidase, transglutaminase, laccase or mixtures thereof are used as water resistance improvers. . By using such agents, the protein adhesive present in the material is further crosslinked, thereby increasing the water resistance of the cured material. Further cross-linking results from chemical denaturation of proteins present in the protein adhesive or by enzyme-catalyzed cross-linking reactions.

  Alternatively, other agents for improving water resistance such as aluminum sulfate can be used.

  Preferably, the degradable material further comprises a hydrophobic component, in particular gum arabic, mastic, colophonium, sandalac or mixtures thereof.

  More preferably, the hydrophobic component may comprise petrolatum, turpentine oil, milk, casein or beeswax.

  Hydrophobic additives increase or adjust the water resistance of the cured material. Thereby it can be exposed to water for a short time without suffering damage, while nevertheless it can be completely dissolved by exposure to water, especially hot water or water vapor, for a longer period of time. The material is manufactured. The above allows, for example, the use of said materials for the production of washable dishes or bowls or shaped parts having a surface that can be wet cleaned.

  Alternatively, the water resistance of molded parts made from said materials can be increased by providing a suitable hydrophobic coating or by painting.

  Preferably, the additive component includes at least one natural colorant. The natural colorant is particularly preferably an iron oxide pigment. By the addition of natural colorants, differently colored shaped parts are produced using the material according to the invention, in which the biological compatibility of the dissolved material is not impaired. Iron oxide pigments allow the material to be colored yellow (yellow iron oxide; CI Pigment Yellow 42), red (red iron oxide: Cl Pigment Red 101) and black (black iron oxide; Cl Pigment Black 11) To do. Furthermore, the use of iron oxide as a colorant causes a more rapid oxidation of stabilizers, in particular linseed oil or boiled linseed oil, where molded parts made from the material of the invention are even more rapidly mechanically mechanical. Become stable.

  Along with iron oxide pigments, other natural colorants may also be incorporated into the material depending on the desired color, for example copper sulfate, copper acetate or cochineal red (C.l. Acid Red 18).

  Furthermore, artificial colorants can also be incorporated into the material, thereby causing the dissolved material to have to be processed individually, depending on the environmental compatibility of the colorant.

  The additive component further preferably comprises at least one blowing agent, preferably sodium bicarbonate. Depending on the blowing agent, the density of the material may be reduced by the introduction of gasses, in particular carbon dioxide. Depending on the amount of blowing agent, the number of gas inclusions may vary. When the number of gas inclusions is large, the soundproofing coefficient or the thermal insulation coefficient of the material increases.

  Other preferred antifoaming agents are sodium carbonate decahydrate, poly (oxyethylene) sodium dodecyl sulfate, ammonium carbonate and potassium carbonate.

  Alternatively, the material can be foamed by other methods, for example by introducing carbon dioxide, nitrogen or other driving gases under pressure, for example during the extrusion process.

  Preferably, the additive component comprises at least one biopolymer. Said at least one biopolymer is preferably lignin, chitin, polycaprolactone, thermoplastic starch, cellulose acetate, polylactic acid, casein, polyhydroxybutyric acid, polyhydroxyalkanoate, cellulose hydrate, cellulose acetate, cellulose acetate Contains butyrate, dextrose, dextrin or mixtures thereof. The addition of biopolymers changes the processing properties of the material, such as fluidity, cure speed, pot life or adhesion. In addition, the properties of the molded parts molded from the material, such as elasticity, mechanical strength, mass and chemical resistance, can also be varied with aim.

  It should be noted that some biopolymers such as colophonium, mastic or sandalac may have a hydrophobic action at the same time, ie they may be used as a hydrophobic component or as part thereof.

  Preferably, the additive component includes an inorganic filler. Said inorganic filler comprises in particular wollastonite, talc, magnesium oxide or mixtures thereof.

  Further preferred inorganic fillers include mica, kaolinite, montmorillonite, calcium carbonate and perlite or mixtures thereof.

  Inorganic fillers prevent shrinkage or distortion (Verzug) of molded parts made from the material. Furthermore, the fire resistance of the material can also be enhanced by the inorganic filler. Alternatively, other inorganic fillers can be used.

  Lithium silicate, sodium silicate or potassium silicate (especially used as amorphous water glass) and colloidal silicon dioxide and lignin sulfonate not only cause favorable effects in the materials of the present invention, but also It has the essential advantage of causing a modification of the rheological properties, water resistance and cure rate.

  The further one viewpoint of this invention is related with the manufacturing method of the shaping | molding member from a degradable material. In the material of the present invention, first, the degradable material is charged in a liquid state according to the above description. Subsequently, a molded member is produced from the degradable material by press processing, particularly molding press, extrusion, blow molding, rotational molding, casting, injection molding, vacuum molding or 3D printing. Finally, the molded member is cured.

  The degradable material of the present invention is liquid or at least fluid based on the components used. Thereby, the degradable material is formed into an arbitrary shaped part, which after hardening has a wood-like appearance based on the natural fibers used. Furthermore, it has been found that the degradable material of the present invention can be used as a substrate for 3D printers. In 3D printing, the material of the present invention can be used in liquid form, depending on the fused deposition modeling. For use in printers operating with multi-jet modeling methods (also called polyjet modeling), the material is pre-dried and crushed into a powder. The powder is then added in a 3D printer, where water is used as a binder.

  Preferably, the produced molded part is irradiated with UV light during or after curing. The UV light preferably has a wavelength of 200 nm to 280 nm, particularly preferably 253 nm.

  By irradiation with UV light, the proteins present in the protein adhesive may be denatured on the surface of the molded part and cross-linked with each other. Thereby, the water resistance of the molded member can be further increased.

  By “curing” is understood in the sense of the present application a process in which the degradable material is solidified by a chemical process or a setting process after the formation of the molded part. Curing begins immediately after extrusion, pressing, molding or printing of the molded member and continues until the molded member molded from the material is shape stable. With the materials of the present invention, the cure time is typically up to 2 days, where a cure time of less than 1 hour can be achieved depending on the composition of the material.

  Preferably, the cured molded member is further dried until the water content of the cured material is less than 1 weight percent. Particularly preferably, the molded part is further dried to a water content of less than 0.2 percent by weight.

  It has been found that a further drying step can further increase the water resistance of the cured material. Without wishing to be bound by theory, this effect is possibly due to the reduction of the water content to less than 1 percent by weight, which forms additional intermolecular amide bonds of proteins present in the protein adhesive, thereby This is due to the fact that the degree of crosslinking can be increased additionally.

  A further aspect of the invention relates to a method for introducing a three-dimensional form into a casting material, preferably concrete. In this case, before casting the casting material, a three-dimensional form of negative mold (Negativabdruck) from the degradable material is provided on the inner wall of the mold or formwork (Schalung). Particularly preferably, the negative mold is provided on the inner wall of the mold or form by 3D printing. After casting and curing of the material, the mold or form is removed and the negative mold from the degradable material is dissolved by exposure to hot liquid or hot vapor. Particularly preferably, the negative mold is dissolved by hot water or steam.

  Thereby, a complicated three-dimensional form is introduced into, for example, a concrete wall without much effort. In particular, it is much easier to introduce undercut grooves in the concrete wall by the method of the present invention. In order to remove all the negative mold from the degradable material, the negative mold may be exposed to a hot liquid under pressure.

  The further viewpoint of this invention is related with the manufacturing method of the degradable material of this invention. In the first step, the binder component is produced by mixing a protein adhesive and water. Thereafter, the natural fibers as well as any additive components that may be present are mixed with the binder component in an agitator. As the stirrer, a planetary stirrer is preferably used. Alternatively, other agitators such as compounders can be used. Finally, the hygroscopic inorganic material is mixed.

  Substances present in the additive component are mixed individually into the material. Alternatively, however, all substances of the additive component may be mixed first, where this mixture is subsequently added to the binder component and the natural fiber.

  Preferably, for the production of the binder, the protein adhesive and water are heated to a temperature between 60 ° C. and 80 ° C., preferably between 65 ° C. and 70 ° C. before or during mixing. Upon heating, the protein adhesive becomes liquid and is mixed with water.

  Preferably, prior to incorporation of the hygroscopic inorganic material, the resulting mixture is dried and processed into a powder. An intermediate product is obtained by mixing the hygroscopic inorganic material. Immediately before use of the material, an amount of water corresponding to 25-200 parts by weight of the amount used for the production of the binder component is incorporated into the intermediate product.

  This method is particularly well suited for the production of the degradable material of the present invention for use in 3D printers working in response to multi-jet modeling methods. In this case, the powder is mixed with water in a printer and placed on a suitable substrate. By this method, a powdery intermediate product is produced even on a large scale, which may then be packaged and stored in small portions having a predetermined amount. Only before the material is processed into a molded part is the powdered intermediate product mixed with a suitable amount of water. When subdividing the intermediate product, the amount of water must be adapted according to the subdivision size. Variations in the amount of water added can further vary the viscosity and consistency of the material.

  Further preferred embodiments and feature combinations of the present invention are apparent from the following detailed description and the entire claims.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings used for the description of the embodiments show the following:

FIG. 1 illustrates a method for producing a degradable material of the present invention. FIG. 2 illustrates an alternative manufacturing method.

  Basically, the same elements have the same reference numbers in the drawings.

Method of Implementation of the Invention FIG. 1 illustrates a manufacturing method for the material 10 of the present invention. First, the protein adhesive 1 is mixed with water 2 in a planetary stirrer while being heated to 65 ° C. to 70 ° C. to obtain a binder component 3. Under further stirring, the natural fiber 4 is first added to the binder component 3. Subsequently, the additive component and the hygroscopic inorganic material 7 are mixed in the form of powder. The substances used in additive component 5 may be added individually and sequentially to the material, or they may first be all mixed together and subsequently the resulting mixture may be added to the material. The decomposable material 10 that can be obtained in this way may subsequently be processed in the processing step 11 by pressing, extrusion, blow molding, rotational molding, casting, injection molding or vacuum forming into a molded member.

  FIG. 2 shows a further alternative manufacturing method for the degradable material 10 as a schematic diagram. Protein adhesive 1 as well as water 2 are heated to 65-70 ° C. in a planetary stirrer and mixed together to form binder component 3. Natural fiber 4 and additive component 5 are mixed. In a subsequent drying step and powdering step 6, the mixture is dried and processed to a particle size of about 0.05 mm. The powdering is preferably carried out in a crusher. Mix hygroscopic inorganic material into powder. The intermediate product 8 thus obtained may be stored for a long time. The intermediate product 8 can also be divided into portions and packaged for later use. Immediately before use, the intermediate product 8 is mixed with an amount of water 9 corresponding to 25-200% by weight of the amount of water 2 used to produce the binder component. The degradable material 10 thus obtained may be processed into a molded member in a subsequent processing step 11, for example, by a 3D printer.

Example 1
In the first example, 30 g of water was cold mixed with 38 g of rabbit glue and subsequently heated to 65 ° C. in a water bath. 17 g of softwood fibers having a length of 0.3 mm to 1 mm and 7 g of glycerin were mixed with this binder component. This mixture was filled in the rear funnel of an extender screw pump (Extenderschneckenpumpe) and 8 g of gypsum powder was continuously added to the conveyed mixture through the front funnel. This material was extruded through a nozzle having a diameter of 2 mm at a pressure of about 6 bar into strands. The extruded material may subsequently be further processed, for example by pressing. Alternatively, elongated shaped members having various cross-sections can also be produced by extrusion through suitable nozzles, which can be cut to the desired length with a knife or saw before or after curing.

Example 2
In the second example, 36 g of rabbit glue was mixed in 28 g of boiling water and stirred to produce a binder component. 7 g of glycerin was added to the binder component. 15 g of softwood fibers having a length of 0.7 mm to 3.5 mm, 0.6 g of iron oxide powder as a colorant and 7.4 g of gypsum powder are added to the binder component, and the resulting material is mixed with a planetary stirrer. Mix well. Just prior to use of the material, 5 g of boiled linseed oil was added. The material was then poured into a mold and pressed at a low temperature for 20 minutes with a pressure of ² kg / cm ² to form a molded part.

Example 3
In a third example, 26 g of water was mixed with 33 g of rabbit glue, left for 30 minutes, and subsequently heated to 70 ° C. in a water bath to produce a binder component. Subsequently, 33 g of nutshell granules were mixed and mixed vigorously in a planetary stirrer. The resulting material was dried and subsequently crushed into powder having an average particle size of about 0.05 mm in a crusher. By incorporating 8 g of gypsum powder, a storage stable intermediate product was obtained. The intermediate product was subsequently filled as a substrate in a 3D printer (3DSystems ZPrinter (c) 150) working according to the multi-jet modeling method, where 26 g of water was used as binder.

Example 4
A degradable material with increased water resistance was obtained in the following fourth example:
For the binder component, 21 g of water was cold mixed with 21 g of Glutinleim and subsequently heated to 65-70 ° C. in a water bath. Thereafter, 2g of alum was added to the binder. As a filler (Zuschlagstoff), 10 g of natural wood fibers having a length distribution of 0.7 to 1.2 mm were added. Compared to the material produced in Examples 1-3, the material showed increased water resistance.

Example 5
In a fifth example, 21 g of water was cold mixed with 21 g of glutin glue and subsequently heated to 65-70 ° C. in a water bath. Thereafter, 3 g of damar dissolved in ethanol to form a paste was added and the solution was mixed. As a filler, 10 g of natural wood fiber having a length distribution of 0.7 to 1.2 mm was added. Compared to the material produced in Examples 1-3, the material showed increased water resistance.

Example 6
In the sixth example, 21 g of water was cold mixed with 21 g of glutin glue and subsequently heated to 65-70 ° C. in a water bath. As a filler, 10 g of natural wood fiber having a length distribution of 0.7 to 1.2 mm was added. Subsequently, 8 g of silicon dioxide was added to the solution. Compared to the material produced in Examples 1-5, the material showed a faster cure time.

Example 7
In the seventh example, 21 g of water was cold mixed with 21 g of glutin glue and subsequently heated to 65-70 ° C. in a water bath. As a filler, 10 g of natural wood fiber having a length distribution of 0.7 to 1.2 mm was added. Subsequently, 5 g of pearlite was added to the mixture as an inorganic filler. Compared to the material produced in Examples 1-6, the material showed better shrinkage behavior.

Claims (16)

  Protein adhesive from at least one protein (1) 10-60% by weight, natural fiber (4) 2-50% by weight, at least one hygroscopic inorganic material (7) 2-15% by weight, water (2) 10 Biodegradable material-derived degradable material comprising -55% by weight and additive component (5) 0-50% by weight.   The degradable material according to claim 1, wherein the protein adhesive (1) contains glutin, collagen, alginate, albumin, gelatin, chondrin, agar, xanthan or a mixture thereof.   The natural fiber (4) comprises wood fibers, cereal fibers, nutshell fibers, glass fibers, corn meal, cellulose fibers, cellulose aggregates or mixtures thereof, particularly preferably coniferous fibers. 2. The degradable material according to 2.   4. The hygroscopic inorganic material (7) according to claim 1, wherein calcium sulfate, calcium oxide, magnesium sulfate, zeolite or a mixture thereof is used, preferably in the form of a powder. Degradable material.   The additive component (5) is 1 to 10% by weight, preferably 2 to 8% by weight of at least one biodegradable plasticizer, preferably glycerin, urea, citric acid triethyl ester, sorbitol, xanthan or alkyl citrate. The decomposable material according to any one of claims 1 to 4, further comprising:   Said additive component (5) comprises 0.1 to 10% by weight, preferably 3 to 6% by weight of at least one biodegradable stabilizer, preferably lignin sulfonate, linseed oil or boiled linseed oil. The decomposable material according to any one of claims 1 to 5, characterized in that:   0.1 to 10% by weight of the additive component (5), preferably tannin, corilagin, potassium alum, ganidine, urea, casein, ferulic acid, gossypol, enzyme such as lysyl oxidase The degradable material according to claim 1, comprising transglutaminase, laccase, or a mixture thereof.   The additive component (5) comprises 0.1 to 10% by weight of at least one hydrophobic component, in particular gum arabic, mastic, colophonium, sandalac or mixtures thereof. The degradable material of any one of Claims.   The additive component comprises at least one biopolymer, preferably lignin, chitin, polycaprolactone, thermoplastic starch, cellulose acetate, polylactic acid, casein, polyhydroxybutyric acid, polyhydroxyalkanoate, cellulose hydrate, cellulose acetate 9. The degradable material according to any one of claims 1 to 8, wherein the degradable material comprises tartar, cellulose acetobutyrate, dextrose, dextrin or a mixture thereof.   The degradable material according to any one of claims 1 to 9, wherein the additive component comprises an inorganic filler, in particular wollastonite, talc, magnesium oxide or a mixture thereof. Next step a) Preparing the degradable material according to any one of claims 1 to 10 in a liquid state,
b) a step of producing at least one molded member by pressing, extruding, blow molding, rotational molding, casting, injection molding, vacuum molding or 3D printing the degradable material;
c) curing the molded member;
A method for producing at least one molded member.   12. Method according to claim 11, characterized in that the material is further irradiated with UV light, in particular with UV light having a wavelength of 200 nm to 280 nm, preferably 253 nm, during or after curing of the shaped part.   13. A method according to claim 11 or 12, characterized in that, after curing, the material is further dried until the cured material has a water content of less than 1% by weight, in particular less than 0.2% by weight. Next Step a) A step of providing a three-dimensional shape negative mold from the degradable material (10) according to any one of claims 1 to 10 on an inner wall of a mold or a mold,
b) pouring a casting material into the mold or form and curing the casting material;
c) removing the mold or form, and d) dissolving the negative mold from the degradable material (10) by exposing it to hot water or steam.
A method of introducing a three-dimensional form into a casting material, preferably concrete. A method for producing a degradable material according to any one of claims 1 to 10,
Next Step a) A step of producing a binder component (3) by mixing the protein adhesive (1) and water (2),
b) mixing natural fiber (4) and additive component (5) with binder component (3) in a stirrer, preferably a planetary stirrer; and c) mixing a hygroscopic inorganic material (7). Including said method.   Before mixing the hygroscopic inorganic material (7), the resulting mixture is dried and processed into a powder, and the intermediate product (8) is obtained by adding the hygroscopic inorganic material (7). 16. The product according to claim 15, characterized in that immediately before its use, water (9) is mixed in an amount corresponding to 25-200% by weight of the amount of water (2) used for the production of the binder component. Method.

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